Extrapolation of Rainflow Matrices

An important area in mechanical engineering is fatigue of materials. The load process is an essential parameter in fatigue design, and is often summarized in the so-called rainflow cycle matrix. Extrapolation of a load measurement to longer distances is needed, and hence one is interested in estimating the limiting rainflow matrix (i.e. the ergodic distribution). An interesting fact is that counting rainflow cycles is equivalent to counting crossings of intervals. The main result is an asymptotic expression for the intensity of interval upcrossings as the upper and lower levels tend to ±, where it is assumed that the point processes of upcrossings of the upper and lower levels converge to two independent Poisson processes. The asymptotic expression only involves the intensity of upcrossings of the upper and lower levels. When estimating the limiting rainflow matrix from a load measurement, the asymptotic result is used where it is valid, i.e. for large interval crossings, and kernel smoothing is used elsewhere. To use the asymptotic result, one needs to extrapolate the level upcrossings for high and for low levels, where it is suggested to use peak over threshold methods. An algorithm for the estimation is given in detail. The usefulness and validity of the asymptotic result is illustrated by several examples, both from simulated processes and measured signals from an automobile.     

The optimal differentiation basis and liftings of

There is an optimal way to differentiate measures when given a consistent choice of where zero limits must occur. The appropriate differentiation basis is formed following the pattern of an earlier construction by the authors of an optimal approach system for producing boundary limits in potential theory. Applications include the existence of Lebesgue points, approximate continuity, and liftings for the space of bounded measurable functions - all aspects of the fact that for every point outside a set of measure , a given integrable function has small variation on a set that is ``big' near the point. This fact is illuminated here by the replacement of each measurable set with the collection of points where the set is ``big', using a classical base operator. Properties of such operators and of the topologies they generate, e.g., the density and fine topologies, are recalled and extended along the way. Topological considerations are simplified using an extension of base operators from algebras of sets on which they are initially defined to the full power set of the underlying space.

     

Concise semisynthesis of novel phenazine-vitamin E hybrids via regioselective tocopheryl ortho-quinone formation

A regioselective method for the semisynthesis of phenazine derivatives has been disclosed through an efficient IBX mediated ortho-quinone formation from vitamin E derivatives. High chemo- and regio-selectivity was observed during the oxidation step and the corresponding 5,6-ortho-quinones could react with various phenylenediamines. Thus, this methodology proves its interest as a concise semisynthetic pathway to phenazine-vitamin E hybrids with moderate to good yields.     

Use of porous graphitic carbon for the analysis of nitrate ester, nitramine and nitroaromatic explosives and by-products by liquid chromatography-atmospheric pressure chemical ionisation-mass spectrometry

A new LC/MS method was developed for the analysis of sixteen different analytes including the most common organic explosives encountered in forensic investigations. The separation was achieved using a porous graphitic carbon (PGC) column with a binary gradient elution. Molecular modeling suggested a possible interpretation for the elution order of explosive compounds on PGC. The introduction of ammonium formate in the mobile phase resulted in the formation of characteristic adduct ions thus enhancing the mass spectrometric detection of nitrate ester and nitramine compounds. Atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI) were compared in terms of sensitivity. The final LC/APCI-MS method allowed easy identification of investigated compounds with limits of detection ranging from 0.04 to 1.06 ng/microl. The analysis of simulated forensic samples confirmed the performance of the method.     

Sorption of silicates on goethite, hematite, and magnetite: experiments and modelling

Sorption of H(4)SiO(4) (including experiments as a function of time, K(d) measurement with different m/v ratios and sorption edges) onto different iron (hydro)oxides as goethite (alpha-FeOOH), hematite (alpha-Fe(2)O(3)), and magnetite (Fe(3)O(4)) has been studied with concentration of silicates under solubility limit. A surface complexation model has been used to account for sorption edge of silicates onto these iron oxide surfaces. It reveals that two types of surface complex namely FeH(3)SiO(4) and FeH(2)SiO(4)(-), are needed to describe properly the experimental observations.     

Identification and relative quantification of adenosine to inosine editing in serotonin 2c receptor mRNA by CE

A new method has been developed allowing the identification and relative quantification of different forms of mRNA after RNA editing. This method was applied to the serotonin 2c receptor mRNA that potentially exhibits 32 different forms after adenosine to inosine editing at five different sites located in a row of 13 nucleotides. CE was used to characterize fluorescently labeled ssDNA molecules on the basis of their conformational polymorphism. The relative amount of these 32 mRNA forms has been estimated by measuring the fluorescence intensity of each individual DNA strand. Accuracy of quantification was established by diluting one form into another or into a mixture of cDNA, showing linear and precise proportion of each form (0.06 相似文献   

Line intensity measurements of methane’s \nu _3-band using a cw-OPO

We report on absolute line strength measurements of P(1), R(0) and R(1) singlet lines in the \(3.3\,\upmu\hbox {m}\,\nu _{3}\) (C–H stretching) band of methane \(^{12}\hbox {CH}_4\) at reference temperature \(T=296\)  K. Line strength measurements are performed at low pressure \((P \le 1\hbox { Torr})\) using direct absorption spectroscopy technique based on a widely tunable continuous-wave singly resonant optical parametric oscillator. The \(1\sigma \) overall accuracy in line strength determinations ranges between 7 and 8 % mostly limited by pressure and frequency measurements. A comparison with previous reported values is made. Our results show good agreement with the HITRAN 2012 database.     

500 GHz mode-hop-free idler tuning range with a frequency-stabilized singly resonant optical parametric oscillator

A 1064 nm pumped continuous-wave, mid-IR (3-4 μm), signal-wave resonant optical parametric oscillator is frequency stabilized at the kilohertz jitter level to the transmission peak of an external high-finesse Fabry-Perot cavity. Owing to the high stability of the resonator length against acoustical perturbation, fine pump tuning of the idler wave around 3.3 μm results in an unprecedented mode-hop-free continuous scan over 500 GHz (17 cm?1).     

A tetrapyridine ligand with a rigid tetrahedral core forms metal-organic frameworks with PtS type architecture

A new tetradentate, pyridine ligand with a rigid tetrahedral core can be prepared in good yield by a cross-coupling methodology. Two metal organic framework structures of Cu(II) with PtS-type topology having a carbon atom as the tetrahedral node have been characterized utilising this ligand.     

Revisiting the photophysical properties and excited singlet-state dipole moments of several coumarin derivatives

The solvent effects on the electronic absorption and fluorescence emission spectra of several coumarins derivatives, containing amino, N,N-dimethyl-amino, N,N-diethyl-amino, hydroxyl, methyl, carboxyl, or halogen substituents at the positions 7, 4, or 3, were investigated in eight solvents with various polarities. The first excited singlet-state dipole moments of these coumarins were determined by various solvatochromic methods, using the theoretical ground-state dipole moments which were calculated by the AM1 method. The first excited singlet-state dipole moment values were obtained by the Bakhshiev, Kawski-Chamma-Viallet, Lippert-Mataga, and Reichardt-Dimroth equations, and were compared to the ground-state dipole moments. In all cases, the dipole moments were found to be higher in the excited singlet-state than in the ground state because of the different electron densities in both states. The red-shifts of the absorption and fluorescence emission bands, observed for most compounds upon increasing the solvent polarity, indicated that the electronic transitions were of π-π* nature.